Classifications

• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
  • A61Q19/00—Preparations for care of the skin
• • A—HUMAN NECESSITIES
  • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
  • A23L—FOODS, FOODSTUFFS OR NON-ALCOHOLIC BEVERAGES, NOT OTHERWISE PROVIDED FOR; PREPARATION OR TREATMENT THEREOF
  • A23L29/00—Foods or foodstuffs containing additives; Preparation or treatment thereof
  • A23L29/20—Foods or foodstuffs containing additives; Preparation or treatment thereof containing gelling or thickening agents
  • A23L29/206—Foods or foodstuffs containing additives; Preparation or treatment thereof containing gelling or thickening agents of vegetable origin
  • A23L29/238—Foods or foodstuffs containing additives; Preparation or treatment thereof containing gelling or thickening agents of vegetable origin from seeds, e.g. locust bean gum or guar gum
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
  • A61K8/00—Cosmetics or similar toiletry preparations
  • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
  • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
  • A61K8/73—Polysaccharides
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
  • C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
  • C08B37/006—Heteroglycans, i.e. polysaccharides having more than one sugar residue in the main chain in either alternating or less regular sequence; Gellans; Succinoglycans; Arabinogalactans; Tragacanth or gum tragacanth or traganth from Astragalus; Gum Karaya from Sterculia urens; Gum Ghatti from Anogeissus latifolia; Derivatives thereof
  • C08B37/0087—Glucomannans or galactomannans; Tara or tara gum, i.e. D-mannose and D-galactose units, e.g. from Cesalpinia spinosa; Tamarind gum, i.e. D-galactose, D-glucose and D-xylose units, e.g. from Tamarindus indica; Gum Arabic, i.e. L-arabinose, L-rhamnose, D-galactose and D-glucuronic acid units, e.g. from Acacia Senegal or Acacia Seyal; Derivatives thereof
  • C08B37/0093—Locust bean gum, i.e. carob bean gum, with (beta-1,4)-D-mannose units in the main chain branched with D-galactose units in (alpha-1,6), e.g. from the seeds of carob tree or Ceratonia siliqua; Derivatives thereof
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L5/00—Compositions of polysaccharides or of their derivatives not provided for in groups C08L1/00 or C08L3/00
  • C08L5/14—Hemicellulose; Derivatives thereof
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10S516/00—Colloid systems and wetting agents; subcombinations thereof; processes of
  • Y10S516/924—Significant dispersive or manipulative operation or step in making or stabilizing colloid system
  • Y10S516/928—Mixing combined with non-mixing operation or step, successively or simultaneously, e.g. heating, cooling, ph change, ageing, milling

Definitions

• the present invention relates to a carob bean gum (or locust bean gum) having a weight-average molecular mass ( M w ) of between 2.5 ⁇ 10 5 and 1.5 ⁇ 10 6 g/mol, at least 60% by weight of said gum being soluble in an aqueous medium at a temperature equal to or less than 60° C., to its method of preparation and to its use.
• M w weight-average molecular mass
• It also relates to a gelling composition comprising said carob bean gum and at least one hydrocolloid.
• the rheology of aqueous phases is usually modified by glucide derivatives of plant or animal origin.
• glucide derivatives The choice of these glucide derivatives depends, for example, on their cost, their availability, the conditions under which they may be used and the types of compounds in which they may be suitable.
• galactomannans which are nonionic polysaccharides extracted from the albumen of seeds of leguminous plants of which they constitute the storage carbohydrate, are often employed as texture agents.
• carob bean gum This is extracted from the seeds of the carob tree ( Ceratonia siliqua L.) which is a tree with persistent foliage originally from Iran and Asia Minor, but cultivated along the entire Mediterranean littoral.
• Carob bean gum is composed of a main chain consisting of D-mannopyranose units linked in the ⁇ (1-4) position, carrying side branches consisting of a single D-galactopyranose unit in the ⁇ (1-6) position.
• Carob bean gum is in general known for its texturing properties and more particularly for its thickening and stabilizing properties.
• native carob bean gum exhibits satisfactory solubility, that is to say greater than 60% by weight of the gum, only at temperatures above 80° C.
• the object of the present invention is to provide a carob bean gum having properties similar to those of native carobs (for example in terms of texturing, compatibility with other compounds, etc.) and good solubility at temperatures well below the usual temperatures for dissolving native carob bean gums.
• the object of the invention is also to provide a carob bean gum which, at a constant concentration, allows a variable viscosity range to be achieved.
• one subject of the present invention is a carob bean gum having a weight-average molecular mass ( M w ) of between 2.5 ⁇ 10 5 and 1.5 ⁇ 10 6 g/mol, at least 60% by weight of said gum being soluble in an aqueous medium at a temperature equal to or less than 60° C.
• Another subject of the invention is a method of preparing the carob bean gum of the above type.
• Yet another subject of the invention is gelling compositions comprising the carob bean gum of the above type and at least one hydrocolloid.
• the invention relates to food formulations comprising the abovementioned gelling compositions.
• the expression “solubility in an aqueous medium at a temperature equal to or less than 60° C.” means that at a temperature equal to or less than 60° C., in an aqueous medium, the carob bean gum develops 60% of the viscosity that it would have developed if it had been dissolved at temperatures above 80° C.
• aqueous medium denotes a medium which consists partly of water.
• the subject of the invention is firstly a carob bean gum having a weight-average molecular mass ( M w ) of between 2.5 ⁇ 10 5 and 1.5 ⁇ 10 6 g/mol, at least 60% by weight of said gum being soluble in an aqueous medium at a temperature equal to or less than 60° C.
• the solubility of the gum according to the invention may advantageously be at least 70% by weight, and preferably be at least 80% by weight, of said gum.
• solubility levels that is to say at least 60% by weight, advantageously at least 70% by weight and preferably at least 80% by weight of the gum—may be achieved more particularly at temperature one less than 60° C., advantageously between 10° C. and 45° C. and preferably between 15° C. and 30° C.
• these solubility levels are achieved at a temperature that may vary from 20° C. to 25° C.
• the weight-average molecular mass ( M w ) of the gum according to the invention is advantageously between 2.5 ⁇ 10 5 and 1 ⁇ 10 6 g/mol and preferably between 2.5 ⁇ 10 5 and 6 ⁇ 10 5 g/mol.
• GPC gel permeation chromatography
• the viscosity measurement may also give information about the weight-average molecular mass ( M w ).
• M w weight-average molecular mass
• a 1% aqueous solution of the carob bean gum according to the invention has a viscosity of between 15 and 2000 mPa ⁇ s (measured at 20 rpm).
• the viscosity of such a solution is preferably between 15 and 1000 mPa ⁇ s.
• the viscosity may be measured using a BROOKFIELD DV-III viscometer at 25° C. and 20 rpm.
• the weight-average molecular mass ( M w ) of the carob bean gum according to the invention is such that its intrinsic viscosity [ ⁇ ] is greater than 2.3 dl/g.
• This viscosity is measured by means of a U-shaped viscometer of the Ubbelhode type.
• the D-mannopyranose/D-galactopyranose mass ratio (M/G) of the carob according to the invention is between 1 and 5, preferably between 2 and 4. Knowing this ratio constitutes one of the means of characterizing the specimen, although it provides no information about the statistical distribution of the D-galactopyranose branches along the main chain.
• the carob bean gum having the aforementioned characteristics is obtained by reducing the weight-average molecular mass ( M w ) of the native gum. This reduction is in general obtained by scission of the glycosic bonds for the purpose of producing shorter chains which are substantially identical, from the chemical standpoint, to the native gum.
• Another aspect of the invention is the method of preparing the carob bean gum as described above.
• This method comprises the following steps:
• step (i) the hydration of the carob bean gum endosperm is carried out for a time long enough to achieve a degree of hydration of between 50 and 90%.
• the degree of hydration may be calculated, for example, by simply measuring the solids content of the endosperm.
• the carob is in the form of a powder with a water content which is advantageously between 6 and 12%.
• the particle size of this powder may vary depending on the operating conditions. For example, it may vary from 20 to 200 ⁇ m.
• the particle size may be measured by laser diffraction, for example using a Malvern Mastersizer® 2000 laser particle size analyzer.
• the drying/grinding operation is more particularly carried out at a temperature of between 30° C. and 90° C.
• This operation may be carried out in any type of apparatus for simultaneous grinding and drying, such as for example a hammer mill or needle mill.
• the depolymerization of the carob may be carried out by oxidation, by an enzymatic process, or by acid hydrolysis, under the effect of high temperature and pressure and in the presence of an oxidizing agent, or by physical treatment such as, for example, by exposure to gamma-type radiation.
• the depolymerization is carried out by oxidation.
• the oxidation is preferably carried out in an alkaline medium in the presence of an agent of the type belonging to the family of peroxides, such as peracetic acid, H 2 O 2 , etc.
• the depolymerization reaction time depends on the final weight-average molecular mass desired.
• the depolymerization may be carried out in a reactor provided with a mixing system suitable for handling fine powder, that is to say powder with a particle size of around 20 to 200 ⁇ m, so as to prevent the formation of crumbs.
• a mixing system suitable for handling fine powder that is to say powder with a particle size of around 20 to 200 ⁇ m, so as to prevent the formation of crumbs.
• the excess alkalinity may be neutralized by adding, for example, ammonium hydroxide or an acid, such as acetic acid, citric acid, phosphoric acid or sulfuric acid.
• the depolymerized carob may then be dried. This drying may be carried out in any type of apparatus that avoids the formation of agglomerates. For example, a Turbosphere, a needle mill or a flash dryer may be used.
• the final carob bean gum is preferably in the form of a powder. Its water content is advantageously between 6 and 12%.
• the steps may be carried out in any order. However, they are preferably carried out in the order indicated above.
• the carob bean gum according to the invention have physico-chemical characteristics compatible with the definitions of the carob bean gum that are described in “ Food Chemical Codex”, 4th edition, page 768 and in European Union (EU) Directive No. 98/86/CE of Nov. 11, 1998.
• the carob bean gum of the invention may be used as a texture agent, especially as thickeners, stabilizers, gelling agents (capable of forming pseudo-gels) and/or emulsifiers in the field of cosmetics, the dyeing and food industries, the oil industry and the field of cleaning products.
• Said gum is intended more particularly for the food field.
• the carob bean gum of the present invention may form a gel whose physical properties (melting point, gel strength, etc.) may be controlled.
• gel a pseudo-solid (behavior approaching that of a solid) resulting from the at least partial combination of polysaccharide chains dispersed in a liquid.
• G′( ⁇ ) also called the storage modulus
• G′′( ⁇ ) also called the loss modulus
• the mechanical quantities G′( ⁇ ) and G′′( ⁇ ) may be measured using an imposed-strain rheometer operating in oscillatory mode.
• an imposed-strain rheometer operating in oscillatory mode.
• G′( ⁇ ) and G′′( ⁇ ) may also be measured using an imposed-stress rheometer operating in oscillatory mode.
• an imposed-stress rheometer operating in oscillatory mode.
• AR1000® rheometer from TA Instruments.
• the principle of the measurement consists in determining firstly the range of reversible mechanical strain in which the response of the gel to the mechanical stress as a function of said strain is linear. Secondly, the gel is subjected to a fixed value of mechanical strain within the linear range determined above. The rheometer then performs an ⁇ frequency sweep.
• G′( ⁇ ) corresponds to the energy stored by the gel in elastic form, this energy being recoverable.
• a gel is called a true gel when, over the entire range of swept stressing frequencies ( ⁇ ), the G′/G′′ ratio is greater than or equal to 10 and when the value of G′( ⁇ ) is greater than or equal to 10 Pa.
• a gel is called a pseudo-gel when, over the entire range of swept stressing frequencies ( ⁇ ), the G′/G′′ ratio is greater than or equal to 5 and when the value of G′( ⁇ ) is greater than or equal to 1 Pa.
• Another aspect of the present invention relates to gelling compositions comprising carob bean gum according to the invention with at least one hydrocolloid.
• the carob bean gum of the invention by itself or in combination with at least one hydrocolloid can result in a pseudo-gel at a temperature equal to or less than 60° C. It has also been found that, as in the case of the native carob bean gum, the combination of the carob of the invention with at least one hydrocolloid can give true gels by heating to a temperature equal to or greater than 80° C.
• hydrocolloids mention may be made by way of nonlimiting example of xanthan gum, carragheenans, agar, Danish agar, and gellan gum.
• the hydrocolloid is xanthan gum.
• the mass ratio of carob bean gum as defined above to the hydrocolloid(s) is(are) chosen between 5/95 and 95/5, advantageously between 20/80 and 80/20 and preferably between 40/60 and 60/40.
• this mass ratio is 50/50.
• compositions may be obtained by simple mixing of the components, namely the carob and the hydrocolloid or hydrocolloids.
• the components may be mixed in the form of powder and then dissolved. They may also be mixed in the form of solutions. It may also be envisioned to add one of the components in powder form to the other component, which is in solution. In the latter case, it is important to avoid the formation of agglomerates during mixing.
• the invention relates to a method of gelling an aqueous phase, characterized in that a pseudo-gel is formed by the addition of a gelling composition as defined above to said phase, at a temperature equal to or less than 60° C., more particularly less than 60° C., advantageously between 10° C. and 45° C. and preferably between 15° C. and 30° C., and after a sufficient rest time.
• the addition of the gelling composition may be carried out at a temperature that may vary from 20° C. to 25° C.
• the invention also extends to the method of gelling an aqueous phase, characterized in that a true gel is formed by the addition of a gelling composition as defined above to said phase, at a temperature equal to or greater than 80° C., and [lacuna] a sufficient rest time.
• the addition of the gelling composition to the aqueous phase will take place at temperatures equal to or greater than 80° C., a cooling step will possibly be necessary.
• a person skilled in the art is capable of determining the suitable rest time depending on the desired G′( ⁇ ) and G′′( ⁇ ) values.
• the amount of the gelling composition that can be used will depend on the aqueous phase to be gelled. This amount may represent from 0.01 to 10%, advantageously from 0.5 to 2% and preferably from 0.8 to 1.5% by weight, of the gelled phase.
• the gelling composition is introduced in the form of a solid or in the form of an aqueous solution.
• gelling compositions may be used in the oil, agrochemical, food, paper and textile industries, as well as in paints and domestic or industrial cleaning agents.
• the gelling compositions are intended for food formulations.
• compositions of the following types jellies, custards, cup custards, aspic, cold jellied poultry, bavaroises, yogurts, ice creams, sorbets, crèmes Listeées, drinks, etc.
• the intrinsic viscosity and the weight-average molecular mass ( M w ) are determined in the following manner:
• a 1% weight/weight solution of the carob according to the invention is prepared by vigorous stirring in demineralized water. The solution is then left to stand at about 25° C. for 24 h. By centrifuging for 1 h at 14 000 rpm, the supernatant liquid is recovered and filtered on glass wool. This mother liquor is then used to prepare solutions of lower concentrations by dilution in demineralized water.
• the reduced viscosities, and then specific viscosities, are then calculated at 25° C. with a U-shaped viscometer of the Ubbelhode type by measuring the drop times.
• the weight-average molecular mass is determined by gel permeation chromatography using polyethylene oxide standard solutions as calibration standards.
• a carob bean gum having a viscosity, after being dissolved at a temperature greater than or equal to 80° C., similar to the carob bean gum of example 1 was obtained.
• the level of solubility of this gum was substantially less than 60% by weight. This gum had the following characteristics:
• the gelling composition of example 3 was prepared by mixing, in a 50/50 weight ratio, the following two powders: the carob bean gum of example 1 and xanthan gum (RHODIGELTM 200 sold by Rhodia).
• true gels were obtained with a native carob (MEYPRO-FLEURTM 200, sold by Meyhall AG)/xanthan gum (RHODIGELTM 200, sold by Rhodia) mixture (50/50 weight ratio), said true gels having the following characteristics (total concentration of gums of 1%. weight/weight in a 1% weight/weight KCl solution):
• the interaction between the carob bean gum of the invention and the xanthan gum is greatly favored compared with the native carob bean gum (this is because, for the same amount of carob bean gum according to example 1 and of the native carob bean gum, the same gel strength is obtained, whereas the BROOKFIELD viscosity developed by the native carob bean gum is appreciably higher: 3000 mPa ⁇ s at a concentration of 1% weight/weight; dissolved at a temperature above 80° C.; BROOKFIELD viscosity measured at 25° C. and 20 rpm).
• carob bean gum of example 1 were to be replaced with native carob bean gum, a firmer custard, less pleasant in one's mouth, was obtained.

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• Health & Medical Sciences (AREA)
• Chemical & Material Sciences (AREA)
• Life Sciences & Earth Sciences (AREA)
• Polymers & Plastics (AREA)
• General Health & Medical Sciences (AREA)
• Veterinary Medicine (AREA)
• Public Health (AREA)
• Animal Behavior & Ethology (AREA)
• Engineering & Computer Science (AREA)
• Organic Chemistry (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• Biochemistry (AREA)
• Materials Engineering (AREA)
• Dermatology (AREA)
• Molecular Biology (AREA)
• Emergency Medicine (AREA)
• Botany (AREA)
• Dispersion Chemistry (AREA)
• Nutrition Science (AREA)
• Food Science & Technology (AREA)
• Birds (AREA)
• Epidemiology (AREA)
• Jellies, Jams, And Syrups (AREA)
• Cosmetics (AREA)
• Polysaccharides And Polysaccharide Derivatives (AREA)
• Glass Compositions (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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• General Preparation And Processing Of Foods (AREA)
• Seeds, Soups, And Other Foods (AREA)
• Meat, Egg Or Seafood Products (AREA)
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• Pyridine Compounds (AREA)

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• 2000
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• 2001
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• 2008
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